Anti-rust material and plug valve lubricant



'15 perior methods of lubricating plug valves.

Patented June 7, 1938 ANTI-RUST MATERIAL AND PLUG VALVE LUBRICANT Frederick H. MacLaren, Calumet City, and Lawrence C. Brunstrum, Chicago, Ill., assignors to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing. Application May 9, 1936, Serial No. 78,932

8 Claims. -(Cl. 87-9) This invention relates to new and improved compositions of matter for use as anti-rust materials and for use in lubricating plug valves. It also relates to methods of making such compositions of matter and to methods for preventing rusting and for lubricating plug valves.

It is an object of our invention to provide compositions of matter which are highly resistant to acids, which adhere tenaciously to metals, and

10 which are superior plug valve lubricants. It is another object of our invention to provide methods for making such compositions of matter. A further object is to provide new and superior methods of preventing rusting and new and su- Still further objects of our invention will become apparent as the description thereof proceeds.

Many attempts have been made in the past to provide lubricants suitable for use on plug valves in acid service. Such a lubricant must have many necessary, or at least highly desirable, properties. Among these, is the necessity that it have a good body which will permit the lubricant to be pressed into a stick which will be suificiently firm and solid at normal atmospheric temperatures to retain its shape and which will at the same time be sufficiently plastic to flow into the space between the cock and body of a plug valve. The lubricant must necessarily have a true grease-like structure and cannot be a mere soap-thickened oil. A still more necessary property is acid resistance, since when lubricating a plug valve used in acid service it is highly essential that the acids do not attack the lubricant, thereby removing it or injuring its properties as a lubricant. In other words, it must be a good slushing compound or anti-rust material. Possibly the most important property of all, how-.

ever, and certainly the most diflicult to obtain consistently with the other necessary properties, is a high degree of adhesiveness to metal. At the same time the product must be a good lubricant and must not cause the valve to stick. With the plug valve lubricants of the prior art it has been found that when minute pin holes are present in the lubricant film, as is almost invariably the case, the acid will penetrate to the metal, generate hydrogen and/or other gases and thereby lift the surrounding lubricant from the metal. This action known as acid lifting, takes place progressively until ultimately all of the lubricant has been removed.

With the lubricants of our invention no such action occurs. The lubricant is so adhesive that it does not lift from the metal even when subjected to a considerable degree of hydrogen evolution from surrounding bare metal. As an example of this, lubricants made in accordance with our invention have been compared with other lubricants by the following method:

A sheet of iron or other metal is coated on both sides over one-half of its surface with the lubricant to be tested and the sheet is then immersed in a bath of strong mineral acid. With either sulfuric acid or hydrochloric acid the best lubricants of the prior art will be removed rather rapidly either by direct attack of the acid on the lubricant or by the acid lifting heretofore referred to. With the lubricants of our invention, this does not occur. In the case of sulfuric acid,the portion of the metal sheet which is uncoated is removed and thecoated portion re-, mains substantially intact, being fully protected by the lubricant. In the case of hydrochloric acid, which acts somewhat more vigorously than sulfuric, the uncoated half of the metal sheet is eaten away and then the coated half is very gradually eaten away from the inside out. In other words, the acid works upwards from the edge of the metal left bare by the removal of the uncoated portion of the metal, but the lubricant is so extremely tenacious that the exterior surfaces of the coated portion of the metal are completely protected even under these extremely vigorous conditions. In spite of this extreme tenacity to metals the compositions which we have invented are excellent lubricants and do not cause the valves in which they are used to stick.

The essential ingredient of the lubricants which we find will accomplish these purposes is made by the acid treatment of condensation products of materials such as chlorinated parafiin wax with aromatic hydrocarbons, for instance naphthalene, by the use of catalysts, such as aluminum chloride. Condensation products of this type, as made by the processes of one of the present inventors or by similar processes, are known as Pourex" and are described, for instance, in U. S. Patents Nos. 1,963,917 and 1,963,918. Other similar condensation products can be used.

- As pointed out in our co-pending patent application. Serial No. 723,164, such condensation products are more satisfactory than most prior art materials for use as plug valve lubricants and slushingcompounds or as constituents of plug valve lubricants and slushing compounds. However, we have found that by acid treating these condensation products it is possible to produce materials which are outstandingly superior for these uses to the materials which have not been acid treated.

Thus in a series of tests in which various materials were applied'to interiors of tin cans and subjected to concentrated sulfuric acid under similcrlir conditions the following results were note I. Materials which are acid resistant in themselves but obviously unsuitable:

Example-Medicinal white oil.

Action of acid-In a few seconds the acid penetrates the oil film and attacks the tin plating.

II. Materials offered for sale as acid lubricants but which are subject to acid lifting.

ExamplesVarious commercial mixtures of mineral oil, parafiin wax and petrolatum.

Action of acidVery much slower than with white oil, thick layers being quite slow to show 'action. Complete removal in time of the film of lubricant which forms a skin floating on the acid.

III. More resistant materials:

ExamplePourex.

Action of acidPeeling may start at edges after about 10 to 30 minutes and 50% to of the film may ultimately roll back.

IV. Excellent materials:

Example-Acid treated Pourex.

Action of acidThe time necessary for the acid to start acting varies although some action is always noticed after one hour. About 10 to 20% of film is removed after a day or two, but the film is never completely removed.

V. Compounded lubricant:

Example-Composition containing Percent Acid treated "Pourex 55 Air floated asbestos 35 Superla wax 5 Amorphous graphite. 5

Action of acid'-May or may not show v any action at edges. Never more than 5% of area removed. Even the addition of HCl which makes the acid very hot causes' no marked increase in rate or extent of removal.

The acid treatment is preferably accomplished;

by the use of fuming sulfuric acidalthough concentrated sulfuric acid can be used. I prefer to treat with about one'pound of IOU/2% H2804 per gallon of Pourex or similar condensation product. 0.1 to 3 pounds of acid per gallon of condensation product can be used.

The acid treating is preferably carried out either at, elevated temperatures or with the Pourex in light hydrocarbon solution or both. Thus we have used the following'two procedures:

The first consists of treating at 140 F.-l50 F. with 1 pound of 104%% H2804 per gallon of Pourex, settling out excess acid and then neutralizing with NH4OH. The neutralized product is then dissolved in naphtha (4 to 8 volumes per volume of product), settled and/or strained free.

.However, sodium hydroxide and other alkalis can be used.

The agitation necessary in the acid treating step cannot be producedv by use of air blowing without destroying the desired properties of acid treated Pourex. Some sort of oxidation must occur to' cause this change. The use of mechanical agitation (or agitation by means of an inert gas) is vital to the satisfactory production of acid treated- Pourex having the-desired metal wetting properties.

We are not aware why'the acid treating of condensation products such as Pourex should so markedly improve their metal wetting properties and other properties important to slushing compounds and plug valve lubricants. However, the fact is that the acid treating does produce a profound improvement.

Our acid treated Pourex can be used. alone or can be compounded, for instance according to the example given above, and pressed into sticks and applied in this form to a plug valve giving lubrication superior to that obtainable of plug valves used in acid service. This is not true to anywhere near the same extent of the ordinary Pourex or similar condensation products which do not have this property of extremely tenacious adherence to metal and which do not have, in general, the necessary grease body or structure.

Pourex to be satisfactory for use by itself as a. plug valve lubricant should be a relatively solid, grease-like material and not a mere synthetic oil. Preferably it should have a melting or softening point above the temperature at which it is to be used and preferably above F. or still more preferably above F. At the same time it should be plastic rather than hard. The A. S. T. M. penetration can suitably range from about 25 to 70. These same specifications also apply, in general, to the other compositions described below.

We find that the use of our acid treated Pourex alone is not as satisfactory as the use of certain compositions containing it which we have developed, For one thing, acid treated Pourex" is relatively expensive. For another thing, it is difiicult to meet the requisite specifications and there are other disadvantages. We have found that these disadvantages can be overcome by blending various other materials with the Pourex. We prefer to add oil or wax, or both oil and wax. It is highly desirable that the oil and/or wax used should have a very high degree of acid resistance. 7

If an oil is to be used, we prefer to use a mineral lubricating oil which has been strongly treated with sulfuric acid, preferably an oil of the type known as white oil. Thus, for instance, we can use an oil of which not more than about 5% and preferably not more than about 1% is soluble in an excess of 95% sulfuric acid at room temperatures.

As a wax, we prefer to use a refined grade of petroleum wax, for instance, one having a melting point of at least about 125 F. Beeswax is a satisfactory substitute for the paraffin wax and other waxes such as ozokerite, Montan wax, etc. can be used. High melting point paraflin waxes and petroleum waxes in general are satisfactory but we prefer to use a refined grade of very high melting point petrolatum wax known commercially as Superla" wax or its equivalent. Superla wax is a petroleum wax having a melting point of from about 140 F. to about 150 F. or above and having a tacky structure.

One highly important composition made from acid treated Pourex", Superla wax and small quantities of air-floated asbestos and amorphous graphite is as follows:

Example I Percent Acid treated Pourex 55 Air-floated asbestos 35 Superla wax Amorphous graphite 5 Another ingredient which we find highly desirable, but by no means necessary in our compositions, is unreacted chlorinated wax. This chlorinated wax should preferably have a chlorine content of from about 5% to about by weight. Suitable compositions can be made from acid treated Pourex and chlorinated wax alone. Such compositions can range from about 10% acid treated Pourex and about 90% chlorinated wax to about 98% acid treated Pourex and about 2% chlorinated wax. Preferably, however, the chlorinated wax should not entirely replace the oil and/or wax but should be present as an additional constituent. Thus, for example, from about 8% to about 40% Pourex", from about 10% to about 50% oil, and from about 5% to about 50% of wax and any amount of chlorinated wax up to about 50% or 60% can be used. Higher percentages of acid treated Pourex can be'used if economically feasible.

We find that still better results can be obtained by incorporating in any of the above compositions a small amount of very finely divided asbestos, such as air-floated asbestos. Quantities of, for instance, from about 1% to about 65% by weight, and preferably from about to about 45% by weight of the total composition can be used, the other materials being present in the relative proportions previously indicated. The presence of this very finely divided asbestos gives the finished lubricant bulk and structure, makes it easier to press, and gives a stick lubricant. It also acts as a stifiening agent and therefore can be used to reduce the amount of wax otherwise necessary. The asbestos is, of course, acid resistant and does not impair this characteristic of the lubricant. Another highly important feature which the asbestos produces in this type of lubricant is that it gives a body which is not affected by temperature. Lubricants made in accordance with our invention and containing, say, about of air-floated asbestos remain thick at temperatures at least up to' 300 F. and in fact up to the temperatures at which charring commences. When using asbestos it is important that the oil, if any, used in the composition, be a high viscosity oil, preferably one having a viscosity above about 150 seconds Saybolt at 100 F. and preferably above about 250 seconds Saybolt at 100 F. When asbestos is not used low viscosity lubricating oils are satisfactory.

Two satisfactory lubricants and the permissible and preferred ranges of constituents for a plug valve lubricant of this type are as follows:

a Per- Prefl i missible fen-ed range rnngc Permit Percent Percent Percent Acid treated Pourox"... 25 8-100 1040 Lubricating oil (0. g. a white mineral oil having a viscosity of 300 sec. Saybolt 2115100 F.) .Q 25 10 0430 5-40 Wax (c. 2. white Wu. 25 30 (H30 5-40 Asbestos 25 30 0-50 540 prise to 90% acid treated Pourex and 10% to 65% asbestos.

Although the compositions of matter set forth above are particularlyuseful for the lubrication of plugvalves in general, and. most particularly the lubrication of plug valves used in acid service, their properties of acid resistance and extreme tenacity of adhesion to metals are important in other applications and particularly for use in protecting metals from corrosive liquids and gases, i. e. as slushing compounds. They can also be used for the impregnation of gaskets and packings. For these uses a material slightly more fluid than that desirable as a plug valve lubricant is usually preferable and the wax in'the above compositions can sometimes be completely eliminated. Thus, a mixture of from about 10% to about 60% acid treated Pour'ex and from. about 40% to about 90% acid resistant mineral 'oil can be used as a slushingcompound or as an impregnating material. The compositions set forth above using acid treated Pourex, oil and wax and the compositions containing chlorinated wax are also suitable for this purpose.

Percentages as given herein are on a weight basis.

While we have described our invention in connectionwith certain specific embodiments thereof and in connection with certain theories of operation, it will be understood that these are by illustration only and not by way of limitation.

We claim:

1. A composition of matter for use in protecting metals from corrosive agents comprising the following ingredients in about the following percentages by weight:

Per cent Fuming sulfuric acid treated condensation product of chlorinated wax and an arcmatic hydrocarbon 10 60 Acid resistant mineral oil 40-90 2. A composition of matter for use in protecting metals against corrosion comprising the following ingredients in about the following percentages by Weight:

Per cent Fuming sulfuric acid treated condensation product of chlorinated wax and an aromatic hydrocarbon 10-60 An organic vehicle selected from the group consisting of mineral oils and waxes 40-90 3. A composition of matter having approximately the following compositions:

' Per cent Fuming sulfuric acid treated condensation product of chlorinated wax and an aromatic hydrocarbon Air-floated asbestos 35 Wax 5 Graphite 5 5. An acid-resistant, grease-like, metal-adherent composition of matter comprising the following ingredients in about the following percentages by weight:

Per cent Fuming sulfuric acid treated condensation product of chlorinated wax and an aromatic hydrocarbon 10-40 Acid-resistant mineral lubricating 011-..--- 5-40 Refined Wax 5-40 Air-floated asbestos 5-40 6. An acid resistant grease-like metal adherent plug valve lubricant comprising the following ingredients in about the following percentages by weight:

Per cent Fumlng sulfuric acid treated condensation product of chlorinated wax and an arcmatic hydrogen 35-90 Air-floated asbestos 10-65 7. An improved plug valve lubricant having approximately the following composition:

Per cent Fuming sulfuric acid treated condensation product of chlorinated wax and an aromatic hydrocarbon 55 Air-floated asbestos 35 Wax 5 Graphite 5 8. An improved acid resistant metal adherent plug valve lubricant comprising the following ingredients in about the following percentages by weight:

Per cent Fuming sulfuric acid treated condensation product of chlorinated wax and an aro-' I matic hydrocarbon 10-40 Acid resistant mineral lubricating oil 5-40 Air-floated asbestos 5-40 FREDERICK n. MACLAREN. LAWRENCE c. BRUNSTRUM. 

